Process for the continuous dyeing and printing of fibre materials containing ionic groups

ABSTRACT

Pad-steaming process for the continuous dyeing and printing of fibre materials containing ionic groups, from organic solvents, characterised in that the fibre materials are dyed or printed with chlorinated hydrocarbon dyeing baths containing ionic dyestuffs which have been rendered soluble in chlorinated hydrocarbons by the formation of salts or addition products with lipophilic compounds. With the new process, it is possible to produce on fibre materials containing ionic groups strong, level and well developed dyeings and prints in excellent yields.

nited States-Patent 1191 Hildebrand et al.

[ PROCESS FOR THE CONTINUOUS DYEING AND PRINTING OF FIBRE MATERIALSCONTAINING IONIC GROUPS [75] Inventors: Dietrich Hildebrand, Odenthal;Robert Kuth, Cologne, both of Germany [73] Assignee: BayerAktiengesellschaft,

Leverkusen, Germany 22 Filed: Aug. 10,1970

21 Appl. No.: 62,651

[30] Foreign Application Priority Data Aug. 16, 1969 Germany 1941698[52] U.S. Cl 8/54, 8/94, 8/168, 8/174, 8/169 [51] Int. Cl D061) 3/14[58] Field of Search 8/94, 168, 174, 173, 8/178, 6, 54

[56] References Cited UNITED STATES PATENTS 3,510,243 5/1970 Seuret eta1 8/94 X 2,721,111 10/1955 Long et al 8/6X 3,164,449 1/1965 Bux'baum8/6 X 2,274,751 3/1942 Sowter et a1 8/173 3,523,749 8/1970 MacLeod et a18/54.2

1 1 Jan. 15, 1974 3,623,834 11/1971 Seuret et a1 8/173 FOREIGN PATENTSORAPPLICATIONS 682,830 1/1966 Belgium 8/174 454,084 6/1968 Switzerland8/178 R 1,581,325 8/1969 France 8/94 OTHER PUBLICATIONS CQIQLLUEZS, 72ndEl ar 195M91- VZLEPM- 2815 and 2816.

Primary Examiner-Donald Levy Assistant Examiner-T, J. Herbert, .lr.Attorney-Plumley and Tyner [5 7] ABSTRACT 8 Claims, No Drawings PROCESSFOR THE CONTINUOUS DYEING AND PRINTING F FIBRE MATERIALS CONTAININGIONIC GROUPS The invention relates to a pad-steaming process for thecontinuous dyeing and printing of fibre materials containing ionicgroups, from organic solvents; the process is characterised in that thefibre materials are dyed or printed with chlorinated hydrocarbondyebaths containing ionic dyestuffs which have been rendered soluble inchlorinated hydrocarbons by the formation of salts or addition productswith lipophilic compounds.

Chlorinated hydrocarbons suitable for the process according to theinvention are primarily the chlorinated hydrocarbons the boiling pointsof which lie between 40 and 170C, e.g. aliphatic chlorinatedhydrocarbons such as methylene chloride, chloroform, car- .bontetrachloride l l -dichloroethane, 1 ,2- dichloroethane, l,l,l-trichloroethane, 1,1,2- trichloroethane, 1,1 ,l ,2-tetrachloroethane,1,1 ,2,2- tetrachloroethane, pentachloroethane, l-

chloropropane, l,2-dichloropropane, l-chlorobutane, 2-chlorobutane,1,4-dichlorobutane, l-chloro-2- methylpropane, 2-chloro-2-methylpropaneor 4-chloro-2-methylpropane, and aromatic chlorinated hydrocarbons suchas chlorobenzene and chlorotolune. Tetrachloroethylene,trichloroethylene and 1,1,1- trichloropropane have proved particularlysatisfactory.

The fibre materials containing ionic groups, which are to be dyedaccording to the invention comprise:

a. fibre materials containing cationic groups.

These include all natural or synthetic fibre materials which can be dyedwith anionic dyestuffs. These are natural polyamides especially wool andsynthetic polyamides, e.g., poly-c-caprolactam,polyhexamethylene-diamine adipate and poly-wamino-undecanic acid;

b. fibre materials containing anionic groups.

These include all synthetic fibre materials which can be dyed with basicdyestuffs, especially the commercial polyacrylonitrile containinganionic groups such as sulphonic acid, sulphimide, carboxyl and- /orphosphonic acid groups; polyesters modified by carboxyl and/or sulphonicacid groups, such as polyethylene terephthalate,polycyclohexanedimethylene terephthalate; heterogeneous polyestersobtained from terephthalic acid, isophthalic acid and ethylene glycol orfrom terephthalic acid, sulphoisophthalic acid and ethylene glycol;furthermore, copolyether ester fibres obtained from phydroxybenzoicacid, terephthalic acid and ethylene glycol; or polyamides modified bysulphonic acid groups, such as polyhexamethylene adipate,polycaprolactam of poly-w-aminoundecanic acid.

The ionic dyestuffs which have been rendered soluble in chlorinatedhydrocarbons by the formation of salts or addition products withlipophilic compensating ions and serve in the process according to theinvention for the dyeing of fibre materials containing cationic groupscomprise chlorinated hydrocarbon-soluble amine salts and amine additionproducts of dyestuffs containing 1 to 4 carboxyl and/or sulphonic acidgroups.

The dyestuffs containing 1 to 4 sulphonic acid groups from which theamine salts or amine addition products soluble in chlorinatedhydrocarbons are derived, may belong to a variety of dyestuff classes,for example, to

the azo, anthraquinone, phthalocyanine, azine and triphenyl-methanedyestuffs. These dyestuffs may also contain reactive groups.

Suitable amines on which the amine salts or amine addition productssoluble in chlorinated hydrocarbons are based, are primary, secondaryand tertiary monoamines as well as primary, secondary and tertiarypolyamines. Examples of primary, secondary and tertiary monoamines are:optionally substituted aliphatic amines, such as tri-n-propylamine,2-ethyl-hexylamine, dodecylamine, dodecylamine polyglycol ether with 20mol ethylene oxide, hexadecylamine, hexadecylamine polyglycol ether with20 mol ethylene oxide, octadecylamine,

N-methyl-octadecylamine, N-methyl-octadecylamine polyglycol other with10 mol ethylene oxide,

cetylamine,

N,N-dimethyl-dodecylamine, N,N-dimethyl-hexadecylamine, v

N ,N-dimethyl-octadecylamine, N,N-dibutyl-dodecylamine,N,N-di-2-hydroxyethyl-oleylamine,N,N-dimethyl-N-(dodecanoylaminomethyl)-amine,N-methyl-N-2-hydroxyethyl-N-[y- (octadecanoylamino)-propyl]-amine,e-aminocapronic acid butyl ester, e-aminocapronic acid dodecylamide,e-aminoundecanic acid butyl-ester;

technical mixtures of fatty amines, such as coconut fatty amine andsperm oil fatty amines and their ethoxylation and propoxylationproducts; optionally substituted cycloaliphatic amines, such asN,N-dimethyl-cyclohexylamine, N-ethyl-cyclohexylamine,N-2-hydroxyethyl-cyclohexylamine,N,N-bis-(2-hydroxyethyl)-cyclohexylamine,N,N-bis-(2-chloroethyl)-cyclohexylamine, l-cyclohexylamino-propanol-Z,l-cyclohexylamino-propylamine-3 and dicyclohexylamine;

optionally substituted araliphatic amines, such as benzylamine,N,N-dimethyl-benzylamine, N,N-dibenzylamine, N-methyl-N,N-dibenzylamine,

l -amino-1 -phenyl-ethane,

i-amino-2-ethane;

optionally substituted aromatic amines, such as N-ethyl-aniline,

N,N-dimethyl-aniline,

N,N-diethyl-aniline,

N-propyl-aniline, N,N-dipropyl-aniline,

Nbutyl-aniline,

N-isobutyl-aniline, N-(2-chloroethyl)-N-butyl-aniline,N-2-hydroxyethyl-aniline, N-methyl-N-(2hydroxyethyl)-aniline,N-butyl-N-(2-hydroxyethyl)-aniline, N,N-bis-(2-hydroxyethyl)-aniline,N-methyl-N-(2-cyanoethyl)-aniline,

2-aminotoluene,

2-methylamino-toluene, Z-dimethylamino-toluene, 2-ethylamino-toluene,

3-amino-toluene, B-dimethylamino-toluene, 3-ehtylamino-toluene,3-butylamino-toluene, 3(N-ethyl-N-hydroxyethyl )-amino-toluene,S-[N-bis-(ZZ-hydroxyethyl)l-amino-toluene, 3-[N-ethyl-N-(2-dimethylaminoethyl)]-amino toluene,

4-methylamino-toluene, 4-dimethylamino-toluene,

'4-ethylamino-toluene,

4-diethylamino-toluene, N-ethyl-N-benzyl-aniline,3-(N-ethyl-N-benzyl)-amino-toluene, xylidine,

2iso-propyl-aniline, 2-methyl-o-ethyl-aniline, 2,6-diisopropyl-aniline,

4-dodecyl-aniline, N,N dimethyl-4-dodecyl-aniline,5,6,7,8-tetrahydro-naphthylamine-( l l-diethylamino-naphthalene,4,4-diamino-dicyclohexylmethane, optionally substituted heterocyclicamines, such as N-propyl-morpholine, N-hexyl-morpholine,N-dodecyl-morpholine, N-hexadecyl-morpholine, N-dodecyl-piperidine,N-hexadecyl-piperidine, N-dodecyl-imidazole, 2-dodecyl-hydroindole,N-dodecyl-benzimidazole, 2-dodecyl-benzimidazole,l-(B-hydroxyethyl)2-octadecyl-imidazoline,l-(B-octadecanoylaminoethyl)2-octadecylimidazoline.

Examples of primary, secondary and tertiary polyamines are primarilyaliphatic polyamines, such as N-dodecyl-N',N'-dimethyl-ethylene-diamine,N-dodecyl-N',N-diethyl-ethylene-diamine,N-octadecyl-N',N'-diethyl-ethylene-diamine,N-phenyl-N,N'-dimethyl-ethylene-diamine,N-oleyl-N,N'-dimethyl-ethylene-diamine,N-oleyl-N',N'-diethyl-ethylene-diamine, N-dodecyl-N',N'-dimethyl-propylene-diamine-(1,3),N-dodecyl-N',N'-diethyl-propylene-diamine-( l ,3), N-oleyl-N ,N'-dimethyl-propylene-diamine-( 1,3), N-oleyl-N ,N-diethyl-propylene-diamine-(1,3), N-dodecyl-ethylene-triamine,N-dodecyl-ethylene-tetramine, N-octadecyl-ethylene-tetramine.

lf acidic dyestuffs containing reactive groups are used, obviously, onlythose amines are suitable for the formation of salts or additionproducts, which contain no free NH-group.

Ionic dyestuffs which have been rendered soluble in chlorinatedhydrocarbons by the formation of salts or addition products withlipophilic compounds and serve in the process according to the inventionfor the dyeing 6 of fibre materials containing anionic groups compriseall cationic dyestuffs which contain at least one cationic nitrogen atomand the anion of an acid which forms a salt soluble in chlorinatedhydrocarbons with the cationic dyestuff.

The cationic dyestuffs from which the dyestuff salts to be usedaccording to the invention, which contain at least one cationic nitrogenatom and are soluble in chlorinated hydrocarbons are derived, may belongto a variety of dyestuff classes, for example, to the azo,anthraquinone, azine, oxazine, xanthene, methine, triphenyl-methane andphthalocyanine dyestuffs. The dyestuffs include optical brighteningagents, e.g. optical brightening agents from the stilbehe, couinarin,azole, and naphthalimide series.

Anions suitable for the dyestuff salts are: anions of acidic esters ofinorganic acids, such as the dodecyl sulphate, I stearyl sulphate, oleylsulphate, oleic acid sulphate, oleic acid butyl ester sulphate,ricinoleic acid ethyl ester sulphate, ricinoleic acid monoethyl glycolester sulphate, oleic acid ethylamide sulphate, oleic acid ethanolamidesulphate, oleic acid diethanolamide sulphate, oleic acid diisobutylamidesulphate, oleic acid anilicle sulphate,

N-acetyloleylamine sulphate, undecylethylene glycol ether sulphate,tetradecyltriglycol ether sulphate, hexadecyldiglycol ether sulphate,octadecylpentaglycol ether sulphate, N-oleyl-4-aminobutano-Z-sulphateions and anions of organic acids, such as oleic acid-N-dimethylamidesulphonate,

C, -C, -paraffin sulphonate, n-butylbenzene sulphonate, n-amylbenzenesulphonate, N-hexylbenzene sulphonate, n-heptylbenzene sulphonate,diisopropylnaphthalene sulphonate, dibutylnaphthalene sulphonate,di-(diisobutyl-methyl)-naphthalene sulphonate, dibutylphenyl polyglycolether sulphate, n-octylbenzene sulphonate, n-nonylbenzene sulphonate,n-decylbenzene sulphonate, n-dodecylbenzene sulphonate,n-tetradecylbenzene sulphonate, n-hcxadecylbenzene sulphonate,n-octadecylbenzene sulphonate, Z-ethyl-hexylbenzene sulphonate,2-propyl-heptylbenzene sulphonate, 2-butyl-octylbenzene sulphonate,Z-amyl-nonylbenzene sulphonate, dodecyl-(6)-benzene sulphonate andtetrapropylene benzene sulphonate ions; and also the palmitate,stearate, oleate ions.

The amounts in which the dyestuff amine salts or addition products orthe salts of dyestuff bases with aliphatic or aromatic carboxylicorsulphonic acids to be used according to the invention are added to thechlorinated hydrocarbon paddingliquors may vary within wide limits,dependent upon the desired depth of colour; in general, amounts of 5 gm30 g in 1000 g of padding liquor have proved satisfactory.

In the process according to the invention it has frequently proveduseful, in order to increase the viscosity -'of the padding liquors, toadd to the padding liquors about 8 to per cent by weight of water,referred to the weight of the chlorinated hydrocarbons, and 0 to 5 percent by weight, referred to the weight of the ch1orinated hydrocarbons,of emulsifiers which form thickened emulsions with the chlorinatedhydrocarbons when water is added. Suitable thickening emulsifiers arecommercial non-ionic, anion-active, cation-active or zwitterionicemulsifiers, for example, oleic acid ethanolamide, oleyl alcoholeicosaglycol ether, nonylphenol heptaglycol ether, nonylphenoldecaglycol ether, dodecylbenzene sulphonate, stearyl alcohol sulphate,N,N-dimethyl-N-benzyl-N-oleyl ammonium chloride andN,N-dimethyl-N-hexadecyl-N-(2-hydroxy-3- sulpho)-propylbetaine.

Furthermore, the chlorinated hydrocarbon dyebaths may containauxiliaries which further the fixing of the dyestuff and/or improve thequality of the dyeing, for example, the levelness. Auxiliaries whichhave proved satisfactory are, for example, interface-active compoundswhich are soluble in chlorinated hydrocarbons, such as alkylbenzenesulphonates, fatty alcohol sulphates, ethoxylation products of fattyalcohols, alkylphenols, fatty amines, fatty acid amides and fatty acids;furthermore, fatty acid ethanolamides, fatty amine oxides, fatty acidamideamine oxides, as well as mixtures thereof. The quantities in whichthe auxiliaries are added to the dyebath amount to 0 4%, preferably 0.52%, referred to the fibre material to be dyed. Furthermore, the dyebathsmay contain 0.1 2 per cent by weight, referred to the weight of thechlorinated hydrocarbons, of a lower carboxylic acid, suchas formic acidor acetic acid.

The process according to the invention is advantageously carried out byspraying or impregnating the fibre materials with the chlorinatedhydrocarbon liquors, squeezing to a liquor absorption of 60 160%, andthen treating them, optionally after an intermediate drying, withsaturated steam or overheated steam at 100 200C. The fibre materials aresubsequently rinsed with chlorinated hydrocarbons, in order to removethe non-fixed dyestuff, and subsequently dried by blowing with hot air.

The dyestuffs soluble in chlorinated hydrocarbons can be added to thechlorinated hydrocarbons liquors in undissolved form. However, it hasalso proved satisfactory to add them to the chlorinated hydrocarbons inthe form of concentrated, e.g., 25 50%, solutions in chlorinatedhydrocarbons or in organic solvents of unlimited miscibility with thelatter, such as dimethyl formamide, isopropanol, diethylene glycolmonoethyl ether, diethylene glycol monobutyl ether, ethylene glycolmonoisopropyl ether, ethylene glycol monobutyl ether, benzyl alcohol orbutyrolactone.

From Swiss Patent Specification No. 454,084 there is known a process forthe continuous dyeing of textile rhriErTi of synthetic poly amidesrrbfii' organic sol- 7 vents, in which the textile materials are dyed orprinted with dyebaths containing disperse dyestuffs or watersolubledyestuffs in solvent mixtures. Compared with this process, the processaccording to the invention in which dyestuffs soluble in chlorinatedhydrocarbons are used, is superior in that it yields stronger and morebrilliant dyeing and prints, since the good solubility of the dyestuffsto be used according to the invention, in chlorinated hydrocarbons evenwithout the addition of solubilizers enables stable single-phase paddingliquors of high dyestuff concentrations to be prepared. Moreover, theuse of dyestuffs soluble in chlorinated hydrocarbons according to theinvention makes it pos- ,sible to rinse the fibre materials withchlorinated hydrocarbons so that the whole dyeing process can be carriedout without the occurrence of waste water.

With the aid of the process according to the invention it is possible toproduce on fibre materials containing ionic groups strong, lever andwell developed dyevings and prints of outstanding fastness properties inex cellent yields and without the occurrence of waste water, while theoriginal textile fibre properties of the dyed material are retained tothe optimal extent.

The parts given in the following Examples are parts by weight.

EXAMPLE 1 A wool fabric is padded on a foulard with a thickened paddingliquor consisting of 20 parts of the dyestuff of the formula [coconutfatty aminel oas- 2 parts nonylphenol decaglycol ether,

898 parts perchloroethylene and parts of water i with a liquorabsorption of steamed at 102C for 10 minutes, subsequently rinsed threetimes with perchloroethylene at room temperature and dried by blowingwith hot air.

Without the occurrence of waste water, there is obtained a wool fabricwhich is dyed in a level red shade and has a substantiallybetter-appearance than a fabric dyed in an aqueous solution.

EXAMPLE 2 A wool fabric is impregnated with a padding liquor 7 8consisting of l i 2 parts N,N-dimethyl-N-hexadecyl-N-(2-oxy-3-sul- 20parts of the dyestuff of the formula pho)-propyl-betaine,

$03 m Hty- \I CH3 ea K [CH:.(CHz)2nCHz-g -N=N F H\ CH2 a =s40 parts of acompound of the formula a 1 p glacial acetic acid '5 100 parts water and03 HaN-CH2CH2OH 857 parts perchloroethylene with a liquor absorption of100%, dried and steamed at 103C for minutes.

The fabric is subsequently rinsed in perchloroeth- CJHNGSO) ylene at 40Cfor 3 minutes and freed from the adher- 6 parts1,3-bis-(2-ethyl-hexyl)-glycerol e h ing solvent by blowing with air. Aclear brilliant yellow h 20 dyeing is obtained without the occurrence ofwaste wap ate, 2 parts isononyl phenol heptaglycol ether, 2 partsN,N-dimethyl-N-hexadecyl-N-(2-oxy-3-sulpho)-propyl-betaine, EXAMPLE 4 4parts benzyl alcohol, 4 A polyacrylonitrile rope is impregnated with apad- 200 parts water and ding liquor consisting of 756 partsperchloroethylene 20 parts of a dyestuff preparation consisting of witha liquor absorption of 104%, and, without inter- 34 parts f th d t ff fthe formula Mfll CHa aim Q [-1 CH3 CH3 H mediate drying, steamed withsteam at 103C for 15 8 Parts water minut 32 parts benzyl alcohol an Thefabric is subsequently rinsed with a solution at 26 Parts p pf 60C f 1part glacial acetic acid 2 parts of a mixture consisting of 40 P i ofstofik emulslon fonslstmg of? 24.6 parts N,N-dimethyl-N,N-bis-octadecylammo- 1 Part 01816 acld ethanolamlde,

1 part oleylalcohol eicosaglycol ether,

4 parts water and i 6 parts perchloroethylene as well as 939 partsperchloroethylene with a liquor absorption of 100% and, withoutintermediate drying, steamed at 103C for 10 minutes. To remove thenon-fixed dyestuff, the rope is rinsed in per- EXAMPLE 3 chloroethyleneat 45C for 5 minutes and subsequently dried with hot air. A cleargreenish yellow dyeing of good fastness properties is obtained withoutthe occurrence of waste water.

nium chloride 17.5 parts oleic acid heptaglycol ether 57.9 parts ofwater in 45 1600 parts perchloroethylene. After drying, an intense reddyeing is obtained without the occurrence of waste water.

A polyacrylonitrile fabric is padded on a foulard with a thickenedpadding liquor consisting of r 30 parts of a dyestuff preparationconsisting of 17.3 parts of the dyestuff salt of the formula EXAMPLE 5elm e9 7 6 ,]-0H=0HN00m OlZHlbQ-SOJ H I OH: OCH:

25 parts butyrolactone and A fabric of anion-modified polyethyleneterephthal- 57.7 parts perchloroethylene, 65 ate fibres is impregnatedwith a padding liquor consist- 3.5 parts glycerol monoacetate, in of 3.5parts methylglycol acetate, parts of a dyestuff preparation consistingof 3 art nonylphenol decaglyC l th 15.7 parts of the dyestuff of theformula GHQ e 0111.01 1 CH=CHN/ 58.8 parts perchloroethylene and 25.5parts butyrolactone, 1 part glacial acetic acid 40 parts of a stockemulsion consisting of:

1 part oleic acid ethanolamide, 1 part oleyl alcohol eicosaglycol ether,4 parts water and 6 parts perchloroethylene as well as 899 partsperchloroethylene with a liquor absorption of 104% and, withoutintermediate drying, steamed at 115C for minutes. To remove thenon-fixed dyestuff, the fabric is rinsed in perchloroethylene at 45C for5 minutes. It is subsequently dried with hot air. A clear pink dyeing isobtained without the occurrence of waste water.

EXAMPLE 6 cmcnm-o H-0 0 0 lgilm 32 parts of a stock emulsion consistingof:

1 part oleyl alcohol heptadecaglycol ether,

1 part oleic acid etha'nolamide,

4 parts water and 6 parts perchloroethylene as well as 958 partsperchloroethylene with a liquor absorption of 64% and, withoutintermediate drying, steamed at 105C for 10 minutes. The fabric issubsequently rinsed in perchloroethylene at C for 5 minutes and thendried with hot air. A clear blue dyeing of good fastness properties isobtained without the occurrence of waste water.

EXAMPLE 7 A yarn of p0lyhexamethylene-diamine adipate threads is sprayedin stripes with a dyestuff solution consisting of parts of a dyestuffpreparation consisting of 15 parts of the dyestuff of the formula andparts diethylene glycol monobutyl ether in 950 parts trichloroethylenedried and steamed at l03C for 15 minutes. The yarn is subsequentlyrinsedin trichloroe'thylene at 45C for 5 minutes and then dried byblowing with hot air. A clear yellow unlevel dyeing of good fastnessproperties is obtained without the occurrence of waste water.

1 1 l2 and 85 parts diethylene glycol monobutyl ether in ing pointbetween 40C and 170C;

950 parts trichloroethylene 3. up to by weight of water based on saidchloand, without intermediate drying, steamed at 103C for rinatedhydrocarbon solvent; and I minutes. The combed material is subsequently4. 0 to 5% by weight based on said chlorinated hyrinsed intrichloroethyleneat 45C for 5 minutes and 5 dro r n lvent f anemulsifier which forms then dried by blowing with hot; air. A cleargreen unat c e em sion in the presence of water level dyeing of goodfastness properties is obtained. d rina d hydrocarbon Solvent;

B. subjecting the fiber material to a treatment with r r steam.

EXAMPLE 9 l0 2. The process of claim 1 in which the fiber material Afabric of poly-e-caprolactam is impregnated with a is subjected to anintermediate drying step before the padding liquor consisting of steamtreatment step (B).

3.0 parts of the fluorescent dyestuff of the formula 3. The process ofclaim 1 in which the fiber material 1 part oleic acid ethanolamide, isrinsed with o nated hydrocarbon solvent to re- 1 part oleyl al h l h t dl l ether, move non-fixed dyestuff subsequent to the steam treat- 4parts water and p I 99] parts trichloroethylene 4. The process of claim1 m which said fiber material with a liquor absorption of 64% andsteamed at 105C P W001} f polyamldel p y y onitrilecontainfor 15minutes. The fabric is subsequently rinsed in tri- 8 amomc groupsSelected t Sulflnlc aCld, sulfichloroethylene at room temperature for 4minutes, ii carboxyl and P acld p p y ers then centrifuged and freedfrom the adhering solvent wit carboxyl or Sulfomc acld groups; orpolyamlde with sulfonic acid groups.

5. The process of claim 1 in which the pad-liquor contains in additionto the amine salt or addition prod- Waste Wateruct (l) andthe'chlorinated hydrocarbon solvent (2);

We claim: I (3) an auxiliary which assists in the fixing of the dye- 1.Pad steaming process for the continuous dyeing Stuff and printing offiber material containing ionic groups comprising the steps of A.impregnating said fiber material which is selected from the groupconsisting of natural polyamides, synthetic polyamides, anionicallymodified synthetic polyamides, anionically modified polyacrylo- 40-nitrile and anionically modified polyesters with by blowing with hotair. A strongly and evenly bright- 3O ened white fabric is obtainedwithout the occurrence'of 6. The process of claim 1 in which thepad-liquor contains in addition to the amine salt or addition product(1) and the chlorinated hydrocarbon solvent (2); (3) an auxiliary whichimprovesthe levelness of the dyeing.

7. The process of claim 1 in which the pad-liquor pad liquor consistingessentially of a Solution of contains in addition to the amine salt oraddition prodl a salt or addition product of a p p y uct (1) and thechlorinated hydrocarbon solvent (2);

pound and an ionic dyestuff having the opposite (3) 0.1 to 2 percent byweight of a lower carboxylic charge of the ionic groups on Said fibermaterial; acid based on the weight of chlorinated hydrocarbon solvent.

2. organic solvent said organic solvent consisting of The fiber materiald by the process of claim a chlorinated hydrocarbon solvent having aboil-

2. organic solvent said organic solvent consisting of a chlorinated hydrocarbon solvent having a boiling point between 40*C and 170*C;
 2. The process of claim 1 in which the fiber material is subjected to an intermediate drying step before the steam treatment step (B).
 3. The process of claim 1 in which the fiber material is rinsed with chlorinated hydrocarbon solvent to remove non-fixed dyestuff subsequent to the steam treatment step (B).
 3. up to 10% by weight of water based on said chlorinated hydrocarbon solvent; and
 4. 0 to 5% by weight based on said chlorinated hydrocarbon solvent of an emulsifier which forms a thickened emulsion in the presence of water and chlorinated hydrocarbon solvent; B. subjecting the fiber material to a treatment with steam.
 4. The process of claim 1 in which said fiber material is wool; synthetic polyamide, polyacrylonitrile containing anionic groups selected from sulfinic acid, sulfimide, carboxyl and phosphonic acid groups; polyesters with carboxyl or sulfonic acid groups; or polyamide with sulfonic acid groups.
 5. The process of claim 1 in which the pad-liquor contains in addition to the amine salt or addition product (1) and the chlorinated hydrocarbon solvent (2); (3) an auxiliary which assists in the fixing of the dyestuff.
 6. The process of claim 1 in which the pad-liquor contains in addition to the amine salt or addition product (1) and the chlorinated hydrocarbon solvent (2); (3) an auxiliary which improves the levelness of the dyeing.
 7. The process of claim 1 in which the pad-liquor contains in addition to the amine salt or addition product (1) and the chlorinated hydrocarbon solvent (2); (3) 0.1 to 2 percent by weight of a lower carboxylic acid based on the weight of chlorinated hydrocarbon solvent.
 8. The fiber material dyed by the process of claim
 1. 